Compounds useful as pigments containing one or more 2,2,6,6-tetraalkylpiperidine groups

ABSTRACT

A pigment, which retains a crystal or particulate structure throughout a process of coloration of a substrate, containing one or more 2,2,6,6-tetraalkylpiperidien groups.

According to the invention there is provided a pigment, which retains acrystal or particulate structure throughout a process of colouration ofa substrate, containing one or more 2,2,6,6-tetraalkylpiperidine groups.

For the avoidance of doubt, pigments are distinct from dyes. The DryColour Manufacturers Association (DCMA) have given a definition ofpigments that differentiates them from dyes as follows.

Pigments are defined as "coloured, black, white or fluorescentparticulate organic or inorganic solids, which are usually insoluble inand essentially physically and chemically unaffected by the vehicle orsubstrate in which they are incorporated. They alter appearance byselective absorption and/or by scattering of light. Pigments are usuallydispersed in vehicles or substrates for application as, for instance, inthe manufacture of inks, paints, plastics or other polymeric materials.Pigments retain a crystal or particulate structure throughout thecolouration process."

Dyes have been defined, by the Dyes Environmental and ToxicityOrganisation (DETO) as "intensely coloured or fluorescent organicsubstances only, which impart colour to a substrate by selectiveabsorption of light. Dyes are . . . soluble and/or go through a processwhich, at least temporarily, destroys any crystal structure of thecolour substances. Dyes are retained in the substrate by absorption,solution and mechanical retention or by ionic or covalent chemicalbonds." (Abstracted from an article appearing in American Ink Maker,June, 1982).

Preferred pigments according to the invention are those of formula I orII ##STR1## in which R is hydrogen, C₁₋₈ alkyl, C₃₋₁₀ alkenyl, phenyl,phenyl-C₁₋₄ alkyl or --COR_(5a) where R_(5a) is hydrogen,--C(R_(10a))═CH₂, C₁₋₆ alkyl, phenyl, --COOC₁₋₄ alkyl or --NR₂₁ R₂₂,where R_(10a) is hydrogen or C₁₋₄ alkyl; R₂₁ is hydrogen, C₁₋₁₂ alkyl,C₅₋₆ cycloalkyl, phenyl, phenylC₁₋₄ alkyl or C₁₋₁₂ alkylphenyl and R₂₂is C₁₋₁₂ alkyl or hydrogen;

each R₁ independently is --CH₃ or --CH₂ (C₁₋₄ alkyl) or both groups R₁form a group --(CH₂)₅ --;

each R₂ independently is --CH₃ or --CH₂ (C₁₋₄ alkyl) or both groups R₂form a group --(CH₂)₅ --;

R₄ is a direct bond or a bridging group; and

R₅ is hydrogen or C₁₋₄ alkyl; or

R₄ and R₅ together with the carbon atom to which they are attached forman isocyclic or heterocyclic bridging group;

R₆ is --NH₂, mono or di-C₁₋₄ alkylamino, C₁₋₂ alkylcarbonylamino,benzoylamino, hydrogen, OH or --CO--C₁₋₄ alkyl or --CO--C₁₋₄ alkoxy; and

R₇ is hydrogen or C₁₋₄ alkyl or

R₆ and R₇ together with the carbon atom to which they are attached forman isocyclic or heterocyclic ring;

R₈ is a direct bond or a bridging group;

D is a residue of a pigment; and

n is an integer from 1 to 4 inclusive.

For the avoidance of doubt, where a symbol appears more than once in aformula, its significances are independent of one another, unlessindicated to the contrary.

When R₄ and R₅ together with the carbon atom to which they are attachedform a heterocyclic or isocyclic ring, this ring is preferably a groupof formula (a) or (b) ##STR2## the starred atom being attachd to D.

When R₄ is a bridging group this is preferably --NHCO--, --NHSO₂ --,--NH--CO--O--, --NH--COCH₂ O--, --NHCOCO--, --NHCOCONH--, --NHCOCOO--,--OCO--, --OSO₂ --, --OCOCO--, --OCO--CO--O--, --OCONH-- or --OCOCONH--.

When R₈ is a bridging group, this is preferably --CO--, --CH₂ CO--,--OCH₂ CO-- or --SO₂ --.

When R₆ and R₇ together with the carbon atom to which they are attachedform a heterocyclic or isocyclic ring, this ring is preferably a groupof formula (c) or (d) ##STR3## where R₁₂ is hydrogen, C₁₋₄ alkyl or C₁₋₄alkoxycarbonyl-C₁₋₃ alkyl.

Preferably D is pigment residue of the azo, perinone, perilene,quinophthalone, isoindolinone, dioxazine, acetoacetyl amine,phthalocyanine or pyrrolo-pyrrole series.

When D is a pigment of the azo series, R₄ or R₈ of the compound offormula I or II respectively, may be attached either to the diazocomponent or to the coupling component. Preferably when D is a pigmentresidue of the azo series, it is a monoazo or disazo pigment residue.

More preferably D is D' where D' is a group of formula III to VIII whenmonovalent ##STR4## or D' is a group of formula IX to XV, when divalent##STR5## or D' is a group of the formula XVI, when trivalent ##STR6## orD' is a group of the formula XVII, when tetravalent ##STR7## in which D₁is 1,3- or 1,4-phenylene, unsubstituted or mono or di-substituted bysubstituents selected from the group consisting of chloro, bromo, C₁₋₂alkyl, C₁₋₂ alkoxy, carboxy or C₁₋₄ alkoxy-carbonyl; or 1,4, -1,5- or1,8-anthraquinone, unsubstituted or mono or disubstituted bysubstituents selected from the group consisting of chloro, bromo,hydroxy, C₁₋₃ alkoxy or acylamino;

D₂ is phenyl, unsubstituted or substitutued by one to threesubstituents, selected by the group consisting of chloro (max. 2), bromo(max. 2), C₁₋₂ alkoxy (max 2), C₁₋₄ alkoxy carbonyl (max 2) andacylamino (max 1);

D₃ is a 4,4'-diphenylene group, unsubstituted or substituted by one tofour substituents selected from chloro, bromo, C₁₋₂ alkyl and C₁₋₂alkoxy or is a group of formula ##STR8## where the starred atoms areattached to the azo in a group of formula VIII

K₁ is a group of any one of formula K_(1a) to K_(1f) ##STR9## where thestarred atom is attached to the azo group of IV or X; and R₁₆ is --O--or --NH--;

K₂ is a group of any one of formula K_(2a) to K_(2c) ##STR10## K₃ is agroup of any one of formula K_(3a) to K_(3g) ##STR11## in which R₁₀ ishydrogen, chloro, bromo, C₁₋₃ alkoxycarbonyl, C₁₋₂ alkyl, C₁₋₂ alkoxy ornitro;

R₉ is 1,4-phenylene, unsubstituted or substituted by one or two groupsselected from chloro, bromo, methyl or C₁₋₂ alkoxy; -4,4'-diphenylene;1,4- or 1,5-naphthylene or a group of the formula ##STR12## where A is--CH₂ --, --NHCO--, --NHCONH--, --NH--CO--CO--NH-- or ##STR13## R₁₁ ismethyl, --COOH or --COOC₁₋₄ alkyl; and R₁₇ is --OH, methyl orunsubstituted phenyl.

By the term "acyl" is preferably meant formyl, --COC₁₋₄ alkyl, --COC₁₋₄alkoxy, or --CO--COO--C₁₋₄ alkyl. When D₁ or D₂ is substituted byacylamino, it is preferably --COC₁₋₄ -alkyl or --COC₁₋₄ alkoxy.

Preferably each R₁ and each R₂ is --CH₃.

Preferably R is R' where R' is hydrogen, methyl, formyl, C₁₋₄alkylcarbonyl or --CO--CO--OC₁₋₄ alkyl.

Preferably R₄ is R₄ ' and R₅ is R₅ ' where R₄ ' is --NH--CO-- or--NH--CO--CH₂ --O-- and R₅ ' is hydrogen; or

R₄ ' and R₅ ' together with the carbon atom to which they are attachedform a group of formula (a) or (b) defined above.

Preferably R₆ is R₆ ' and R₇ is R₇ ' where R₆ ' is --NH₂, mono- ordi-C₁₋₄ alkylamino, C₁₋₂ alkylcarbonylamino or benzoylamino and R₇ ' ishydrogen; or

R₆ ' and R₇ ' together with the carbon atom to which they are attachedform a group of formula (c) or (d) defined above.

R₈ is preferably R₈ ' where R₈ ' is a direct bond or --CO--, --CH₂ CO--,--OCH₂ CO-- or --SO₂ --.

Preferably R₁₀ is R₁₀ ' where R₁₀ ' is hydrogen, methyl, chloro, bromo,C₁₋₂ alkoxy (max. 1 on a phenyl ring), or C₁₋₃ alkoxycarbonyl (max. 1 ona phenyl ring).

More preferably R₁₀ is R₁₀ " where R₁₀ " is hydrogen, methyl, chloro,bromo, or methoxy (max. 1 on a phenyl ring).

Preferred compounds of formula I are of formula XX ##STR14## in which R,R₁ and R₂ are as defined above;

either both groups R₂₀ are of formula (e) or both groups R₂₀ are offormula (f) ##STR15## where the starred atom is attached to the --NHgroup;

R₁₃ is hydrogen, chloro, bromo, methyl, ethyl, C₁₋₂ alkoxy or C₁₋₄alkoxycarbonyl;

R₁₄ is hydrogen, chloro, bromo or methyl;

R₁₅ is --CO--NH*--, --CO--O*-- or --SO₂ NH*--; the starred group beingattached to the 2,2,6,6-tetraalkyl-piperidine group.

R₁₈ is 1,4-phenylene, unsubstituted or substituted by 1 or 2 groupsselected from chloro, bromo, methyl, ethyl, methoxy and ethoxy;4,4'-diphenylene, each phenylene group being unsubstituted orsubstituted by 1 or 2 groups selected from chloro, bromo, methyl, ethyl,methoxy and ethoxy; or unsubstituted 1,4- or 1,5-naphthalene. Compoundsof formula I or II can be prepared by reacting 1 mol of a compound offormula XXV

    D-R.sub.30                                                 (XXV)

with n moles of a compound of formula XXVI or XXVII ##STR16## where oneof R₃₀ and R₃₁ is --COCl or Cl and the other is --R₄ --H or one of R₃₀and R₃₁ is --R₄ --Cl and the other is hydrogen; and

one of R₃₀ and R₃₂ is --COCl or Cl and the other is --R₈ --H or one ofR₃₀ and R₃₁ is --R₈ --Cl and the other is hydrogen and the other symbolsare as defined above.

Preferably where D is of the azo series, the above reaction is carriedout at elevated temperatures, more preferably 80° to 150° C. Preferablywhere D is of the azo series the reaction is carried out in the presenceof an inert solvent such as C₁₋₄ alkylbenzene, halobenzene or a highboiling liquid hydrocarbon.

Preferably where D is of the quinophthalone series, the above reactionis carried out at lower temperatures more preferably 10°-40° C., mostpreferably room temperature (about 25°).

Preferably where D is of the perylene or perinone series, the reactionis carried out at elevated temperatures, preferably from 100° to 240° C.

Preferably where D is of the acetoacetylamine series the above reactionis carried out at temperatures from 20° to 100° C.

Preferably where D is of the isoindolinone dioxazine, phthalocyanine orpyrrolo-pyrrole series, the reaction is carried out at a temperature of20° to 100° C.

Further, according to the invention there is provided a compound, foruse in preparing a compound of formula I or formula II where D is of theazo series, of formula XXX or XXXI ##STR17## where R_(a) is the residueof a diazotisable amine or of a coupling component and the other symbolsare as defined above. Preferably R_(a) is naphthyl or phenylunsubstituted or substituted by 1 or 2 groups selected from Cl, Br, OH,NH₂, C₁₋₄ alkoxy, C₁₋₄ alkyl or C₁₋₃ alkoxycarbonyl.

The compounds according to the invention are suitable for pigmentingpolymeric material such as polyethylene, polypropylene, polystyrene,polyvinylchloride, natural rubber and synthetic leather. The compoundsaccording to the invention are also suitable for use in lacquers ofvarious types, for example oil or water based paints. The compoundsaccording to the invention are also suitable for pigmenting in the mass(either in solvent containing or solvent free systems) for example spindyeing of viscose or cellulose acetate. The compounds according to theinvention are also suitable for printing inks, for pigmenting paper andfor applying to coatings of textiles.

The resulting pigmentations have excellent fastness properties to heat,light, weathering, chemicals, migration, bleeding, overlacquering andsolvents. Further, the compounds according to the invention maintaintheir depth of colour and have good application properties, for exampleresistance to flocculation, resistance to crystallisation and fastnessto dispersing.

Polymers to which pigments of the invention are applied are alsostabilised against the effects of U.V. light by the pigments. Thetensile strength of polymer containing a pigment according to theinvention is significantly improved over that of virgin polymer.

The invention will now be illustrated by the following Examples in whichall parts and percentages are by weight and all temperatures are in °C.unless indicated to the contrary.

EXAMPLE 1

61.9 Parts of 3-amino-4-chloro-benzoic acid-2',2',6',6'-tetra-methyl-piperidinylamide are stirred for 1 hour in 100parts of water and 105 parts of glacial acetic acid at room temperature.This is then reacted with 75 parts of conc. HCl and stirred a furtherhour. The mixture is then cooled to 0°-5° by adding 100 parts of ice andimmersing the reaction vessel in an ice/water bath. 51 parts by volumeof 4N aqueous sodium nitrite solution is added slowly over 15-20 minutesand the mixture is stirred for a further hour, whilst maintaining thetemperature below 5°. The resulting diazonium chloride solution is thenclear filtered.

25.6 Parts of barbituric acid are dissolved in 100 parts of water and 20parts by volume of a 30% aqueous NaOH solution which is thenprecipitated out again in a mixture of 100 parts of water and 21 partsof glacial acetic acid. The suspension is cooled to 0° to 5° and, whilststirring is added over 25 minutes to the diazonium solution which isalso at that temperature. The resultant yellow suspension is stirred for3 hours whilst further cooling, then for one hour at room temperatureand then for a further hour at 80°-85°, filtered and the precipitate iswashed with salt and acid-free water, dried at 80° and milled. A pigmentof the formula 1a ##STR18## results that colours polypropylene a yellowtone and the resulting pigmentations have good fastness properties. Thecoloured polypropylene can also be worked into fibres having goodtensile strength.

EXAMPLE 2

25.3 Parts of 4,4'-diamino-3,3'-dichloro-1,1'-diphenyl are stirred for 1hour in 60 parts of water and 60 parts of concentrated HCl at roomtemperature and this is then cooled to 0° to 5° by adding 100 parts ofice and immersing the reaction vessel in an ice cold bath. The solutionthat forms is added, whilst stirring, to 51 parts by volume of 4Naqueous sodium nitrite over 15-20 minutes and this is stirred for afurther hour at 0° to 5°. The resulting diazonium solution is then clearfiltered.

57.8 Parts of1-(2',2',6',6'-tetramethylpiperidinyl)-2-hydroxy-4-methyl-5-cyanopyrid-6-one,are dissolved in 200 parts by volume water and 25 parts by volume of a30% solution of aqueous NaOH and by the slow addition of a mixture of100 parts of ice, 100 parts by volume of water and 25 parts by volume ofglacial acetic acid, the pyridone product precipitates out again. Thesuspension that results is then slowly added, over 20-30 minutes at 0°to 5° whilst stirring, to the above-mentioned diazonium solution.

The resulting red suspension is of the pigment of formula 2a ##STR19##

The suspension is stirred for a further 3 hours at 0° to 5° and for afurther hour at 80° to 85°. The suspension is then filtered, theprecipitate is washed with salt and acid-free water and is then driedunder vacuum at 80°.

83.6 Parts of the pigment of formula 2a results, that colourspolypropylene a red tone and the resulting pigmentations have goodfastness properties. The polymer can be worked into fibres having goodtensile strength.

EXAMPLE 3

1.2 Parts of sodium metal are dissolved in 80 parts of methanol. Thesolution is cooled to 20° C. and 12.8 parts of phthalodinitrile areadded. The suspension that results is stirred for 11/2 hours at 20° to25°. 23.5 parts of 4-cyanoacetylamino-2,2,5,6-tetramethyl piperidine areadded and the mixture is stirred at room temperature for 16 hours. 3parts glacial acetic acid are added and a golden yellow intermediateproduct precipitates out which is washed with methanol and water andthen dried under vacuum at 60°.

17.5 Parts of the so formed intermediate product are stirred into 100parts of dimethylformamide and are then reacted with 6.4 parts ofbarbituric acid. A yellow pigment is formed very quickly. After stirringfor 16 hours at 20°-25°, the mixture is heated for a further hour to 80°and then is reacted with 3 parts of glacial acetic acid. The resultingpigment is of formula 3a ##STR20## and at 20° can be filtered off,washed with dimethylformamide and cold water and dried.

After milling, the pigment can be added to plastics materials and tolacquers to colour them yellow and produce pigmentations having goodfastness properties.

EXAMPLE 4

4.8 Parts of zinc acetate dihydrate, 6.5 parts ofperylene-3,4,9,10-tetracarboxylic acid dianhydride and 14.3 parts of3-amino-benzene sulphonic acid-2',2',6',6'-tetramethylpiperidinylamideare heated to 220° in 120 parts of quinoline under a weak nitrogenatmosphere and left at this temperature for 5 hours. After this time, asample, boiled in dilute NaOH solution, shows no free perilenetetracarboxylic acid present.

After cooling to 100°, the mixture is filtered and the residue is washedwith quinoline, methanol and water. The resulting damp presscake isheated to 95° in 100 parts of 2% of aqueous sodium hydroxide, afterwhich it is filtered off and then washed, dried and milled. 9 Parts ofthe pigment of formula 4a ##STR21## where Q is ##STR22## result, whichpigment is a red bordeaux colour and has good properties in plasticsmaterial.

EXAMPLE 5

65.4 Parts of pyromellitic acid dianhydride and 61 parts of3-hydroxy-2-methyl-quinoline-4-carboxylic acid are heated under refluxat 205° in 1000 parts of nitrobenzene for 1 hour, distilling off thewater produced by the reaction. The mixture is held at this temperaturefor 31/2 hours. The mixture is then cooled to 10° and after stirring atthis temperature for 1 hour, is filtered and the product is washed intoluene and ethanol. 93 parts of a dark brown quinophthaloneintermediate result.

90 Parts of this quinophthalone intermediate are stirred homogenouslywith 900 parts of 1-methyl-2-pyrrolidinone for 1 hour. When the mixtureis at about 25°, 42 parts of 4-amino-2,2,6,6,-tetra-methyl-piperidineare added. The temperature rises to about 35°. After the exothermicreaction has terminated, the mixture is heated to 120° over 1 hour andheld for 2 hours at this temperature. The mixture is then refluxed for15 hours, distilling off the water produced by the reaction, after whichit is cooled to room temperature, filtered, washed with a little1-methyl-2-pyrrolidinone and alcohol and then dried. 81 parts of abronze pigment of formula 5a ##STR23## result, that can be used tocolour polypropylene brown and such pigmentations have good fastnessproperties.

EXAMPLE 6

33.45 Parts of a product derived from the coupling of 2 mols ofdiazotised 3-amino-4-chlorobenzoic acid and 1 mol of1,4-bis-acetoacetylamino-2,5-dimethylbenzene are stirred in 300 parts byvolume of ortho-dichlorobenzene and 1 part by volume ofdimethyl-formamide. This is then heated to 100° and slowly reacted with10 parts of thionyl chloride and is then stirred for 2 hours at 100°whereby the suspension thickens. Any excess of thionyl chloride,together with about 20 parts by volume of ortho-dichlorobenzene isdistilled off at 70°-80° under vacuum (20-30 mm of Hg). To the remainingmixture, a solution of 15.5 parts of4-amino-2,2,6,6-tetramethylpiperidine in 80 parts by volume ofortho-dichlorobenzene is added and the mixture is stirred for 2 hours at120°, followed by a further 2 hours at 150°, after which the suspensionis cooled to 80°-100°. The resulting reddish yellow suspension is thenfiltered, washed with orthochlorobenzene (at 80°-100°) until thefiltrate is colourless. After cooling, the ortho-dichlorobenzene isseparated from the filtrate by the addition of methanol, and this isthen washed out of the methanol with water and the resulting pigment isdried.

The resulting pigment is of formula 6a ##STR24## and colourspolypropylene a reddish-yellow tone.

EXAMPLE 7

Example 1 is repeated using, instead of 25.6 parts of barbituric acid,29.0 parts of 1,4-bis-acetoacetylamino-2-methyl-benzene to form thepigment of formula 7a ##STR25##

The pigment of formula 7a colours polypropylene a yellow tone andproduces pigmentations with good fastness properties.

EXAMPLE 8

Example 7 is repeated using (instead of 61.9 parts of3-amino-4-chlorobenzoic acid-2',2',6',6'-tetramethylpiperidinylamide)76.0 parts of 4-amino-2,5-dichlorobenzene sulphonicacid-2',2',6',6'-tetramethyl piperidinylamide. The resulting pigment isof formula 8a ##STR26## which colours polypropylene a yellow tone andproduces pigmentations with good fastness properties. The polypropylenecan also be worked into fibres that have a good tensile strength.

EXAMPLE 9

(i) 38.0 Parts of 4-amino-2,5-dichlorobenzene sulphonicacid-2',2',-6',6'-tetramethylpiperidinylamide in 50 parts of water and50 parts of glacial acetic acid are diazotised according to the methodof Example 1.

To this product 18.8 parts of 2-hydroxy-3-naphthalene carboxylic acid in10 parts by volume of water and 15 parts by volume of a 30% aqueous NaOHsolution are added and coupled according to the method of Example 1. Thecompound of formula 9a ##STR27## results.

(ii) 57.9 Parts of the compound of formula 9a are then stirred into 300parts by volume of 1,2-dichlorobenzene. In order to remove resultantwater, the mixture is distilled at 70°-80° under vacuum and about 30parts by volume of 1,2-dichlorobenzene and water are removed. Themixture is then cooled to 60° and 1 part by volume dimethyl formamideand 10.2 parts by volume of thionyl chloride are added and are stirredfor 3 hours at 100°-110°, whereby SO₂ and HCl are given off in formingthe resulting acid chloride of the pigment of formula 9a.

Then the excess thionyl chloride is distilled off at 70°-80° undervacuum together with 30 parts by volume 1,2-dichlorobenzene.

A solution of 8.9 parts of 1,4-diamino-2,5-dichlorobenzene (thecondensation amine) dissolved in 150 parts by volume of1,2-dichlorobenzene at 100° is added to the acid chloride suspension.The resulting red pigment suspension is stirred for 2 hours at 120° andthen for a further 2 hours at 150°. It is then filtered at 100°, washedwith 400 parts by volume of 1,2-dichlorobenzene at 100°, cooled to roomtemperature and then washed with 500 parts by volume of methanol and 500parts by volume of water. The filter cake is dried and then milled. 59.8parts of a red pigment of formula 9b ##STR28## results, that is good forpigmenting polypropylene fibres in the mass and the resulting fibreshave good tensile strength.

EXAMPLE 10

Example 9 is repeated using 31 parts of 3-amino-4-chlorobenzoicacid-2',2',6',6'-tetramethyl piperidinylamide instead of 38 parts of4-amino-2,5-dichlorobenzene sulphonicacid-2',2',6',6-tetramethylpiperidinylamide.

56.7 Parts of the pigment of the formula 10a ##STR29## result, thatcolours polypropylene red by pigmentation in the mass and producesfibres with good tensile strength.

(ii) The pigment of formula 10a can also be prepared by a methodanalogous with that of Example 1 using 31 parts of3-amino-4-chlorobenzoic acid-2',2',6',6'-tetramethylpiperidinyl amide(instead of 61.9 parts of 3-amino-4-chlorobenzoicacid-2',2',6',6'-tetramethylpiperidinylamide) and 25.9 parts of1,4-bis-(2'-hydroxy-3-naphthoylamino)-2,5-dichlorobenzene (instead of25.6 parts of barbituric acid). Twice as much water is however used inthe step of reacting the diazonium chloride solution with the couplingcomponent and twice as much water is used when adding the glacial aceticacid.

(iii) The pigment of formula 10a can also be made by a method analogouswith that of Example 9(ii) by coupling 2 moles of diazotised3-amino-4-chlorobenzoic acid with 1 mol of1,4-bis(2'-hydroxy-3'-naphthoylamino)-2,5-dichlorobenzene forming theacid chloride with thionyl chloride and condensing this acid chloridewith 2,2,6,6-tetramethyl-4-aminopiperidine.

EXAMPLES 11 TO 14

Compounds of the formula 4a ##STR30## in which R is as given in Table 1below, can be formed by a method analogous to that of Example 4 fromappropriate reactants.

                  TABLE 1                                                         ______________________________________                                                                         Colour                                                                        in                                                                            Poly-                                        Ex.                              propyl-                                      No.  Q                           ene                                          ______________________________________                                        11                                                                                  ##STR31##                  Red                                          12                                                                                  ##STR32##                  Red                                          13                                                                                  ##STR33##                  Red- brown                                   14                                                                                  ##STR34##                  red- violet                                  ______________________________________                                    

EXAMPLES 15 TO 46

Compounds of the formula ##STR35## in which the symbols are as definedin Table 2 below can be prepared by a method analogous to that ofExample 7 from appropriate reagents.

                                      TABLE 2                                     __________________________________________________________________________                                Colour in    pos.                                 Ex.                         polypropy-   of                                   No.                                                                              R     R.sub.13                                                                             R.sub.14                                                                         R.sub.18 lene  R.sub.15                                                                             R.sub.15                             __________________________________________________________________________    15 H     Cl     H  1,4-phenylene                                                                          yellow                                                                              --CONH--                                                                             4                                    16 H     Cl     H  2-chloro-1,4-                                                                          "     "      4                                                       phenylene                                                  17 H     Cl     H  2,5-dichloro-1,4-                                                                      "     "      4                                                       phenylene                                                  18 H     Cl     H  2-methoxy-1,4-                                                                         "     "      4                                                       phenylene                                                  19 H     Cl     H  2,5-dimethoxy1,4-                                                                      reddish-                                                                            "      4                                                       phenylene                                                                              yellow                                            20 H     Cl     H  2-chloro-5-methyl-                                                                     yellow                                                                              "      4                                                       1,4-phenylene                                              21 H     Cl     H  3,3'-dimethyl-4,4'                                                                     yellow                                                                              "      4                                                       diphenylene                                                22 H     CH.sub.3                                                                             H  2,5-dimethyl-1,4-                                                                      "     "      4                                                       phenylene                                                  23 H     --OCH.sub.3                                                                          H  2,5-dimethyl-1,4-                                                                      "     "      4                                                       phenylene                                                  24 H     --COOCH.sub.3                                                                        H  1,4-phenylene                                                                          "     "      4                                    25 H     "      H  2,5-dimethyl-1,4-                                                                      "     "      4                                                       phenylene                                                  26 H     "      H  2-methyl-5-chloro-                                                                     "     "      4                                                       1,4-phenylene                                              27 H     --COOC.sub.2 H.sub.5                                                                 H  2,5-dimethy1-1,4-                                                                      "     "      4                                                       phenylene                                                  28 --COCH.sub.3                                                                        Cl     H  1,4-phenylene                                                                          "     "      4                                    29 "     Cl     H  2,5-dimethyl-1,4-                                                                      "     "      4                                                       phenylene                                                  30 "     Cl     H  2-chloro-5-methyl-                                                                     "     "      4                                                       1,4-phenylene                                              31 "     --COOCH.sub.3                                                                        H  2,5-dimethyl-1,4-                                                                      "     "      4                                                       phenylene                                                  32 "     "      H  2-chloro-5-methyl-                                                                     "     "      4                                                       1,4-phenylene                                              33 "     "      H  1,4-phenylene                                                                          "     "      4                                    34 H     Cl     H  1,4-phenylene                                                                          reddish-                                                                            --SO.sub.2 NH--                                                                      4                                                                yellow                                            35 H     Cl     H  2,5-dimethyl-1,4-                                                                      reddish                                                                             "      4                                                       phenylene                                                                              yellow                                            36 H     Cl     H  2-chloro-5-methyl-                                                                     reddish                                                                             "      4                                                       1,4-phenylene                                                                          yellow                                            37 H     Cl     4-Cl        reddish                                                                             "      3                                                                yellow                                            38 H     Cl     4-Cl                                                                             1,4-phenylene                                                                          reddish                                                                             "      3                                                                yellow                                            39 H     Cl     4-Cl                                                                             2-chloro-1,4-                                                                          reddish                                                                             "      3                                                       phenylene                                                                              yellow                                            40 H     Cl     4-Cl                                                                             2,5-dichloro-1,4-                                                                      reddish                                                                             "      3                                                       phenylene                                                                              yellow                                            41 H     Cl     4-Cl                                                                             2-methoxy-1,4-                                                                         reddish                                                                             "      3                                                       phenylene                                                                              yellow                                            42 H     Cl     4-Cl                                                                             2,5-dimethoxy-1,4-                                                                     reddish-                                                                            "      3                                                       phenylene                                                                              yellow                                            43 H     Cl     4-Cl                                                                             2,5-dimethyl-1,4-                                                                      yellow                                                                              "      3                                                       phenylene                                                  44 H     Cl     4-Cl                                                                             3,3'-dimethyl-4,4'-                                                                    "     "      3                                                       diphenylene                                                45 H     Cl     4-Cl                                                                             1,5-naphthylene                                                                        "     "      3                                    46 H     Cl     1-Cl                                                                             1,4-naphthlene                                                                         "     "      3                                    __________________________________________________________________________

EXAMPLES 47 TO 84

The pigments of Examples 47 to 75 defined in Table 3 can be preparedaccording to the method of Example 9 and the pigments of Examples 75 to84 (defined in Table 4) can be made analogously to the method of Example10 from appropriate reactants.

                                      TABLE 3                                     __________________________________________________________________________                                    Colour in                                     Ex.             Coupling                                                                             Condensation                                                                           polypro-                                      No.                                                                              Diazo Component                                                                            Component                                                                            amine    lene                                          __________________________________________________________________________    47 3-amino-4-chloro-benzene                                                                   2-hydroxy-                                                                           1,4-diamino-                                                                           yellowish-                                       sulfonic acid 2',2',6'-                                                                    3-naphthene                                                                          benzene  red                                              6'-tetramethylpiperidi-                                                                    carboxylic                                                       nyl-amide    acid                                                          48 3-amino-4-chloro-benzene                                                                   2-hydroxy-                                                                           1,4-diamino-2-                                                                         red                                              sulfonic acid 2',2',6'-                                                                    3-naphthene                                                                          chlorobenzene                                             6'-tetramethylpiperidi-                                                                    carboxylic                                                       nyl-amide    acid                                                          49 3-amino-4-chloro-benzene                                                                   2-hydroxy-                                                                           1,4-diamino-2-                                                                         red                                              sulfonic acid 2',2',6'-                                                                    3-naphthene                                                                          chloro-5-                                                 6'-tetramethylpiperidi-                                                                    carboxylic                                                                           methylbenzene                                             nyl-amide    acid                                                          50 3-amino-4-chloro-benzene                                                                   2-hydroxy-                                                                           1,4-diaino-2-                                                                          reddish-                                         sulfonic acid 2',2',6'-                                                                    3-naphthene                                                                          methoxybenzene                                                                         brown                                            6'-tetramethylpiperidi-                                                                    carboxylic                                                       nyl-amide    acid                                                          51 3-amino-4-chloro-benzene                                                                   2-hydroxy-                                                                           3,3'-dichloro-                                                                         red                                              sulfonic acid 2',2',6'-                                                                    3-naphthene                                                                          benzidine                                                 6'-tetramethylpiperidi-                                                                    carboxylic                                                       nyl-amide    acid                                                          52 3-amino-4-chloro-benzene                                                                   2-hydroxy-                                                                           1,4-diamino-2,5-                                                                       "                                                sulfonic acid 2',2',6'-                                                                    3-naphthene                                                                          dichlorobenzene                                           6'-tetramethylpiperidi-                                                                    carboxylic                                                       nyl-amide    acid                                                          53 4-amino-2,5-dichloro-                                                                      2-hydroxy-                                                                           1,4-diamino                                                                            yellowish-                                       benzene sulfonic acid                                                                      3-naphthene                                                                          benzene  red                                              2',2',6',6'-tetra-                                                                         carboxylic                                                       methylpiperidinylamide                                                                     acid                                                          54 4-amino-2,5-dichloro-                                                                      2-hydroxy-                                                                           1,4-diamino                                                                            blueish-                                         benzene sulfonic acid                                                                      3-naphthene                                                                          2-chlorobenzene                                                                        red                                              2',2',6',6'-tetra-                                                                         carboxylic                                                       methylpiperidinylamide                                                                     acid                                                          55 4-amino-2,5-dichloro-                                                                      2-hydroxy-                                                                           3,3'-dichloro-                                                                         red                                              benzene sulfonic acid                                                                      3-naphthene                                                      2',2',6',6'-tetra-                                                                         carboxylic                                                       methylpiperidinylamide                                                                     acid   benzidine                                              56 4-amino-2,5-dichloro-                                                                      2-hydroxy-                                                                           1,5-diamino-                                                                           brown                                            benzene sulfonic acid                                                                      3-naphthene                                                                          naphthalene                                               2',2',6',6'-tetra-                                                                         carboxylic                                                       methylpiperidinylamide                                                                     acid                                                          57 4-amino-2,5-dichloro-                                                                      2-hydroxy-                                                                           1,4-diamino-2-                                                                         red                                              benzene sulfonic acid                                                                      3-naphthene                                                                          methyl-5-chloro-                                          2',2',6',6'-tetra-                                                                         carboxylic                                                                           benzene                                                   methylpiperidinylamide                                                                     acid                                                          58 4-amino-2,6-dichloro-                                                                      2-hydroxy-                                                                           1,4-diamino-                                                                           "                                                benzene sulfonic acid-                                                                     3-naphthene                                                                          benzene                                                   2',2',6',6'-tetra-                                                                         carboxylic                                                       methylpiperidinylamide                                                                     acid                                                          59 4-amino-2,6-dichloro-                                                                      2-hydroxy-                                                                           1,4-diamino-2,5-                                                                       red                                              benzene sulfonic acid-                                                                     3-naphthene                                                                          dichlorobenzene                                           2',2',6',6'-tetra-                                                                         carboxylic                                                       methylpiperidinylamide                                                                     acid                                                          60 4-amino-2,6-dichloro-                                                                      2-hydroxy-                                                                           3,3'-dichloro-                                                                         red                                              benzene sulfonic acid                                                                      3-naphthoic                                                                          benzidine                                                 2',2',6,6'-tetramethyl-                                                                    acid                                                             piperidinylamide                                                           61 4-amino-2,6-dichloro-                                                                      2-hydroxy-                                                                           1,5-diamino-                                                                           brown                                            benzene sulfonic acid                                                                      3-naphtene                                                                           nahthalene                                                2',2',6,6'-tetramethyl-                                                                    acid   naphthalene                                               piperidinylamide                                                           62 2-amino-4,5-dichloro-                                                                      2-hydroxy-                                                                           1,4-diamino                                                                            red                                              benzene sulfonic acid                                                                      3-naphthoic                                                                          benzene                                                   2',2',6,6'-tetramethyl-                                                                    acid                                                             piperidinylamide                                                           63 2-amino-4,5-dichloro-                                                                      2-hydroxy-                                                                           1,4-diamino-2,5-                                                                       "                                                benzene sulfonic acid                                                                      3-naphthoic                                                                          dichlorobenzene                                           2' ,2',6,6'-tetramethyl-                                                                   acid                                                             piperidinylamide                                                           64 2-amino-4,5-dichloro-                                                                      2-hydroxy-                                                                           3,3'-dichloro-                                                                         "                                                benzene sulfonic acid                                                                      3-naphthoic                                                                          benzidine                                                 2',2',6,6'-tetramethyl-                                                                    acid                                                             piperidinylamide                                                           65 2-amino-4,5-dichloro-                                                                      2-hydroxy-                                                                           1,5-diamino-                                                                           brown                                            benzene sulfonic acid                                                                      3-naphthoic                                                                          naphthalene                                               2',2',6,6'-tetramethyl-                                                                    acid                                                             piperidinylamide                                                           66 3-amino-4-chloro-                                                                          2-hydroxy-                                                                           1,4-diamino-                                                                           yellowish-                                       benzoic acid-2',2',-                                                                       3-naphthoic                                                                          benzene  red                                              6',6'-tetramethyl-                                                                         acid                                                             piperidinylamide                                                           67 3-amino-4-chloro-                                                                          2-hydroxy-                                                                           1,4-diamino-2-                                                                         red                                              benzoic acid-2',2',-                                                                       3-naphthoic                                                                          chlorobenzene                                             6',6'-tetramethyl-                                                                         acid                                                             piperidinylamide                                                           68 3-amino-4-chloro-                                                                          2-hydroxy-                                                                           1,4-diamino-2-                                                                         red                                              benzoic acid-2',2',-                                                                       3-naphthoic                                                                          chloro-5-methyl                                           6',6'-tetramethyl-                                                                         acid   benzene                                                   piperidinylamide                                                           69 3-amino-4-chloro-                                                                          2-hydroxy-                                                                           1,4-diamino-2-                                                                         red-brown                                        benzoic acid-2',2',-                                                                       3-naphthoic                                                                          methoxybenzene                                            6',6'-tetramethyl-                                                                         acid                                                             piperidinylamide                                                           70 3-amino-4-chloro-                                                                          2-hydroxy-                                                                           3,3'-dichloro-                                                                         red                                              benzoic acid-2',2',-                                                                       3-naphthoic                                                                          benzene                                                   6',6'-tetramethyl-                                                                         acid                                                             piperidinylamide                                                           71 3-amino-4-carbomethoxy                                                                     2-hydroxy-                                                                           1,4-diamino-                                                                           yellowish-                                       benzoic acid 2',2',6'-                                                                     3-naphthoic                                                                          benzene  red                                              6'-tetramethylpiperi-                                                                      acid                                                             dinylamide                                                                 72 3-amino-4-carboxymethoxy                                                                   2-hydroxy-                                                                           1,4-diamino-2-                                                                         blueish-                                         benzoic acid 2',2',6'-                                                                     3-naphthene                                                                          chlorobenzene                                                                          red                                              6'-tetramethylpiperi-                                                                      carboxylic                                                       dinylamide   acid                                                          73 3-amino-4-carboxymethoxy                                                                   2-hydroxy-                                                                           1,4-diamino-2,5-                                                                       red                                              benzoic acid 2',2',6'-                                                                     3-naphthene                                                                          dichlorobenzene                                           6'-tetramethylpiperi-                                                                      carboxylic                                                       dinylamide   acid                                                          74 3-amino-4-carboxymethoxy                                                                   2-hydroxy-                                                                           3,3'-dichloro-                                                                         red                                              benzoic acid 2',2',6'-                                                                     3-naphthene                                                                          benzidine                                                 6'-tetramethylpiperi-                                                                      carboxylic                                                       dinylamide   acid                                                          75 3-amino-4-carboxymethoxy                                                                   2-hydroxy-                                                                           1,5-diamino-                                                                           brown                                            benzoic acid 2',2',6'-                                                                     3-naphthene                                                                          naphthalene                                               6'-tetramethylpiperi-                                                                      carboxylic                                                       dinylamide   acid                                                          __________________________________________________________________________

                                      TABLE No. 4                                 __________________________________________________________________________    Ex.                                                                              Diazo Component                                                                            Coupling Component                                                                           Nuance                                         __________________________________________________________________________    76 3-amino-4-chlorobenzoic                                                                    2-hydroxy-3-naphthoic acid-                                                                  red                                               acid-2',2',6',6'-tetra-                                                    (4'-benzoylamino)-phenyl-                                                        methylpiperidinylamide                                                                     amide                                                         77 3-amino-4-chlorobenzoic                                                                    5-(2'-hydroxy-3-naphthoyl                                                                    brown                                             acid-2',2',6',6'-tetra-                                                                    amino)-benzimidazolone                                           methylpiperidinylamide                                                     78 3-amino-4-chlorobenzoic                                                                    5-acetoacetylaminobenzimida-                                                                 yellow                                            acid-2',2',6',6'-tetra                                                                     zolone                                                           methylpiperidinylamine                                                     79 3-amino-4-methoxy-                                                                         2-hydroxy-3-naphthoic acid                                                                   red                                               carbonylbenzoic acid                                                                       (4'-benzoylamino)-                                               2',2',6',6'-tetra-                                                                         phenylamide                                                      methylpiperidinylamide                                                     80 3-amino-4-methoxy-                                                                         5-(2'-hydroxy-3'-naphthoyl-                                                                  brown                                             carbonylbenzoic acid                                                                       amino)-benzimidazolone                                           2',2',6',6'-tetra-                                                            methylpiperidinylamide                                                     81 3-amino-4-methoxy-                                                                         5-acetoacetylamino-benzimi-                                                                  yellow                                            carbonylbenzoic acid                                                                       dazolone                                                         2',2',6',6'-tetra-                                                            methylpiperidinylamide                                                     82 4-aminobenzoic acid                                                                        2-hydroxy-3-napthoic acid                                                                    yellowish-                                        2',2',6',6'-tetramethyl-                                                                   2'-methoxy-phenylamide                                           piperidylamide                                                             83 4-aminobenzoic acid                                                                        2-hydroxy-3-naphthoic acid                                                                   scarlet                                           2',2',6',6'-tetramethyl-                                                                   2'-ethoxyphenylamide                                             piperidylamide                                                             84 4-aminobenzoic acid                                                                        2-hydroxy-3-naphthoic acid                                                                   red                                               2',2',6',6'-tetramethyl-                                                                   phenylamide                                                      piperidylamide                                                             __________________________________________________________________________

EXAMPLE 85

(a) 3-aminobenzene sulphonicacid-2',2',6',6'-tetramethyl-piperidinylamide (of Example 4) can beprepared by sulphochlorination and amidation of nitrobenzene with4-amino-2,2,6,6,-tetraalkyl-piperidine followed by reduction with asulphide (e.g. NaS). A white powder having a melting point of 244°-245°results.

(b) 4-(4'-chloro-3'-aminobenzoyl-)amino-2,2,6,6-tetramethyl-piperidinecan be prepared as follows.

A solution of 55.2 parts of 3-nitro-4-chlorobenzoyl chloride in 200parts of volume of toluene is added dropwise to well stirred solution(at room temperature) of 100 parts by volume of toluene, 41 parts of2,2,6,6-tetramethyl-4-aminopiperidine, 1 part of tetrabutyl ammoniumbromide and 120 parts by volume of a 30% aqueous sodium hydroxidesolution.

The mixture is stirred overnight and the resulting precipitate isfiltered off. After washing with toluene and n-hexane, the filtrate isvacuum dried and in order to remove any organic salts present is addedto 1000 parts of water. After a further filtration step and drying, 74parts of 4-(4'-chloro-3'-nitrobenzoyl)amino2,2,6,6-tetramethylpiperidine having a melting point of 166°-168°result.

In order to convert this to the amine, 68 parts of the nitro compoundare added to a mixture of 600 parts by volume of 94% ethanol, 80 partsof iron powder and 16 parts of 30% HCl solution at boiling. Afterboiling for a number of hours, reduction is terminated. After adding 14parts of sodium carbonate, the resulting iron oxide precipitate isfiltered off. After concentrating by boiling under vacuum,4-(3'-amino,4'-chlorobenzoyl)amino-2,2,6,6-tetramethylpiperidineresults.

(c)4-(3'-amino-4-chlorobenzoyl)amino-2,2,6,6-tetramethyl-1-acetylpiperidinecan be prepared as follows:

68 Parts of4-(3'-nitro-4'-chlorobenzoyl)-amino-2,2,6,6-tetramethylpiperidine areadded to 250 parts of acetic anhydride. After the addition of 21 partsof triethylamine, the suspension is stirred for 16 hours at toomtemperature and then for 3 hours at 100°-110°. In order to completeprecipitation of the acetyl derivative, 1500 parts by volume of coldwater are added and stirred at room temperature until all the excessacetic anhydride is destroyed. The precipitate is then filtered, washedneutral with water and dried. 72 parts of4-(3'-nitro-4'-chlorobenzoyl)-amino-1-acetyl-2,2,6,6-tetramethyl-piperidinehaving a melting point of 198°-200° results.

Reduction may then be carried out as described under (b) above as forthe N-unsubstituted tetraalkylpiperidinyl compound with iron in anaqueous alcohol system.

A good yield of4-(3'-amino-4'-chlorobenzoyl)amino-1-acetyl-2,2,6,6-tetramethylpiperidinehaving a melting point of 232°-234° result.

(d) 4-cyanoacetylamino-2,2,6,6-tetramethylpiperidine (in Example 3) canbe produced by reacting 4-amino-2,2,6,6-tetramethylpiperidine with theethyl ester of cyanoacetic acid in the absence of solvent at 90°.

Application Example A

0.05 Parts of the compound of Example 1 are homogenised in a mixingroller mill at 150°-160° for about 8 minutes, with 2 parts ofdibutyl-tin-bis-thioglycollic acid hexyl ester and 50 parts of a mixtureconsisting of 65% polyvinylchloride and 35% diethylhexylphthalate.

The polymer is rolled into a sheet and then is glossed in a doubleroller calender. The resultant transparent sheet has good light fastnessproperties.

Application Example B

Four parts of the compound of Example 1 are added to 96 parts of amixture of:

50 parts of a 60% solution of coco aldehyde-melamine resin of 32% of fatcontent in xylene,

30 parts of a 50% melamine resin solution in butanol,

10 parts of ethylene glycol monoethylether and

10 parts of xylene,

and the mixture ground for 24 hours in a ball mill. The dispersionobtained is sprayed on an aluminum sheet, the spray coating allowed todry in the air for 30 minutes and then stoved for 30 minutes at 120°. Ayellow film with good light and weathering fastness is obtained.

Application Example C

The 990 parts of a commercially available U.V. stabilised polypropylenespin fibre type, 10 parts of the compound of formula 6a are added by adry colouring method over 10 minutes, after which the polymer isextruded. Fibres that have a fibre of 15 d tex are obtained.

Tensile strength comparisons are then carried out on fibres that havebeen exposed for 200, 400, 600 and 800 hours (in a weatherometer).Fibres that have been exposed for 400 hours have a tensile strength of57% of the value of unexposed fibres.

As a comparison polypropylene is coloured with the pigment of Example 2of DAS 1,150,165 under the same conditions and after 400 hours thetensile strength of the fibres is only 20% of the value of the unexposedfibres.

Application Examples A to C can be repeated using an appropriate amountof an other compound of Examples 1 to 6 and 8 to 84.

What is claimed is:
 1. A pigment of formula I or II ##STR36## in which Ris hydrogen, C₁₋₈ alkyl, C₃₋₁₀ alkenyl, phenyl, phenyl-C₁₋₄ alkyl or--COR_(5a) where R_(5a) is hydrogen, --C(R_(10a))═CH₂, C₁₋₆ alkyl,phenyl, --COOC₁₋₄ alkyl or --NR₂₁ R₂₂, were R_(10a) is hydrogen or C₁₋₄alkyl; R₂₁ is hydrogen, C₁₋₁₂ alkyl, C₅₋₆ cycloalkyl, phenyl, phenylC₁₋₄alkyl or C₁₋₁₂ alkylphenyl and R₂₂ is C₁₋₁₂ alkyl or hydrogen;each R₁independently is --CH₃ or --CH₂ (C₁₋₄ alkyl) or both groups R₁ form agroup --(CH₂)₅ --; each R₂ independently is --CH₃ or --CH₂ (C₁₋₄ alkyl)or both groups R₂ form a group --(CH₂)₅ --; R₄ is a direct bond or abridging group; and R₅ is hydrogen or C₁₋₄ alkyl; or R₄ and R₅ togetherwith the carbon atom to which they are attached form an isocyclic orheterocyclic bridging group; R₆ is --NH₂, mono or di--C₁₋₄ alkylamino,C₁₋₂ alkylcarbonylamino, benzoylamino, hydrogen, OH or --CO--C₁₋₄ alkylor --CO--C₁₋₄ alkoxy; and R₇ is hydrogen or C₁₋₄ alkyl or R₆ and R₇together with the carbon atom to which they are attached form anisocyclic or heterocyclic ring; R₈ is a direct bond or a bridging group;D is a residue of a pigment; and n is an integer from 1 to 4 inclusive.2. A pigment according to claim 1, in which D is a pigment residue ofthe azo, perinone, perylene, quinophthalone, isoindolinone, dioxazine,acetoacetylamine, phthalocyanine or pyrrolo-pyrrole series.
 3. A pigmentaccording to claim 1, in which D is D' where D' is a group of formulaIII to VIII when monovalent ##STR37## or D' is a group of formula IX toXV, when divalent ##STR38## or D' is a group of the formula XVI, whentrivalent ##STR39## or D' is a group of the formula XVII, whentetravalent ##STR40## in which D₁ is 1,3- or 1,4-phenylene,unsubstituted or mono or di-substituted by substituents selected fromthe group consisting of chloro, bromo, C₁₋₂ alkyl, C₁₋₂ alkoxy, carboxyor C₁₋₄ alkoxycarbonyl; or 1,4, -1,5- or 1,8-anthraquinone,unsubstituted or mono or disubstituted by substituents selected from thegroup consisting of chloro, bromo, hydroxy, C₁₋₃ alkoxy or acylamino;D₂is phenyl, unsubstituted or substituted by one to three substituents,selected by the group consisting of chloro (max. 2), bromo (max. 2),C₁₋₂ alkoxy (max2), C₁₋₄ alkoxy carbonyl (max 2) and acylamino (max 1);D₃ is a 4,4'-diphenylene group, unsubstituted or substituted by one tofour substituents selected from chloro, bromo, C₁₋₂ alkyl and C₁₋₂alkoxy or is a group of formula ##STR41## where the starred atoms areattached to the azo in a group of formula VIII K₁ is a group of any oneof formula K_(1a) to K_(1f) ##STR42## where the starred atom is attachedto the azo group of IV or X; and R₁₆ is --O-- or --NH--; K₂ is a groupof any one of formula K_(2a) to K_(2c) ##STR43## K₃ is a group of anyone of formula K_(3a) to K_(3g) ##STR44## in which R₁₀ is hydrogen,chloro, bromo, C₁₋₃ alkoxycarbonyl, C₁₋₂ alkyl, C₁₋₂ alkoxy or nitro; R₉is 1,4-phenylene, unsubstituted or substituted by one or two groupsselected from chloro, bromo, methyl or C₁₋₂ alkoxy; -4,4'-diphenylene;1,4- or 1,5-naphthylene or a group of the formula ##STR45## where A is--CH₂ --, --NHCO--, --NHCONH--, --NH--CO--CO--NH-- or ##STR46## R₁₁ ismethyl, --COOH or --COOC₁₋₄ alkyl; and R₁₇ is --OH, methyl orunsubstituted phenyl.
 4. A pigment according to claim 1 of the formulaXX ##STR47## in which R, R₁ and R₂ are as defined in claim 2; eitherboth groups R₂₀ are of formula (e) or both groups R₂₀ are of formula (f)##STR48## where the starred atom is attached to the --NH group; R₁₃ ishydrogen, chloro, bromo, methyl, ethyl, C₁₋₂ alkoxy or C₁₋₄alkoxycarbonyl;R₁₄ is hydrogen, chloro, bromo or methyl; R₁₅ is--CO--NH*--, --COO--O*-- or --SO₂ NH*--; the starred group beingattached to the 2,2,6,6-tetraalkyl-piperidine group. R₁₈ is1,4-phenylene, unsubstituted or substituted by 1 or 2 groups selectedfrom chloro, bromo, methyl, ethyl, methoxy and ethoxy; 4,4'-diphenylene,each phenylene group being unsubstituted or substituted by 1 or 2 groupsselected from chloro, bromo, methyl, ethyl, methoxy and ethoxy; orunsubstituted 1,4- or 1,5-naphthalene.
 5. A process for preparing acompound of formula I or II according to claim 1 comprising reacting acompound of formula XXV

    D--R.sub.30

with a compound of formula XXVI or XXVII ##STR49## in which one of R₃₀and R₃₁ is --Cl or --COCl and the other is --R₄ --H or one of R₃₀ andR₃₁ is --R₄ --Cl and the other is hydrogen, and one of R₃₀ and R₃₂ is--COCl or Cl and the other is --R₈ --H or one of R₃₀ and R₃₂ is --R₈--Cl and the other is hydrogen; and the other symbols are as defined inclaim
 1. 6. A process for colouring a polymeric material comprisingapplying a pigment according to claim 1 to the material.
 7. A pigmentaccording to claim 1 wherein,when R₄ is a bridging group, it is--NHCO--, --NHSO₂ --, --NH--CO--O--, --NH--COCH₂ O--, --NHCOCO--,--NHCOCONH--, --NHCOCOO--, --OCO--, --OSO₂ --, --OCOCO--,--OCO--CO--O--, --OCONH-- or --OCOCONH--; when R₄ and R₅ together withthe carbon atom to which they are attached form a heterocyclic orisocyclic ring, this ring is a group of formula (a) or (b) ##STR50## inwhich the starred atom is attached to D; when R₆ and R₇ together withthe carbon atom to which they are attached form a heterocyclic orisocyclic ring, this ring is a group of formula (c) or (d) ##STR51##where R₁₂ is hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxycarbonyl-C₁₋₃ alkyl; andwhen R₈ is a bridging group, it is --CO--, --CH₂ CO--, --OCH₂ CO-- or--SO₂ --.
 8. A pigment according to claim 2 wherein,when R₄ is abridging group, it is --NHCO--, --NHSO₂ --, --NH--CO--O--, --NH--COCH₂O--, --NHCOCO--, --NHCOCONH--, --NHCOCOO--, --OCO--, --OSO₂ --,--OCOCO--, --OCO--CO--O--, --OCONH-- or --OCOCONH--; when R₄ and R₅together with the carbon atom to which they are attached form aheterocyclic or isocyclic ring, this ring is a group of formula (a) or(b) ##STR52## in which the starred atom is attached to D; when R₆ and R₇together with the carbon atom to which they are attached form aheterocyclic or isocyclic ring, this ring is a group of formula (c) or(d) ##STR53## where R₁₂ is hydrogen, C₁₋₄ alkyl or C₁₋₄alkoxycarbonyl-C₁₋₃ alkyl; and when R₈ is a bridging group, it is--CO--, --CH₂ CO--, --OCH₂ CO-- or --SO₂ --.
 9. A pigment according toclaim 3 wherein,when R₄ is a bridging group, it is --NHCO--, --NHSO₂ --,--NH--CO--O--, --NH--COCH₂ O--, --NHCOCO--, --NHCOCONH--, --NHCOCOO--,--OCO--, --OSO₂ --, --OCOCO--, --OCO--CO--O--, --OCONH-- or --OCOCONH--;when R₄ and R₅ together with the carbon atom to which they are attachedform a heterocyclic or isocyclic ring, this ring is a group of formula(a) or (b) ##STR54## in which the starred atom is attached to D; when R₆and R₇ together with the carbon atom to which they are attached form aheterocyclic or isocyclic ring, this ring is a group of formula (c) or(d) ##STR55## where R₁₂ is hydrogen, C₁₋₄ alkyl or C₁₋₄alkoxycarbonyl-C₁₋₃ alkyl; and when R₈ is a bridging group, it is--CO--, --CH₂ CO--, --OCH₂ CO-- or --SO₂ --.
 10. A pigment according toclaim 3 wherein, in any acylamino substituent on D₁ or D₂, the acylgroup is --COC₁₋₄ alkyl or --COC₁₋₄ alkoxy.
 11. A pigment according toclaim 4 wherein each R₁ and each R₂ is methyl and R is R' where R' ishydrogen, methyl, formyl, C₁₋₄ alkylcarbonyl or --CO--CO--OC₁₋₄ alkyl.12. A pigment according to claim 7 whereinR is R' where R' is hydrogen,methyl, formyl, C₁₋₄ alkylcarbonyl or --CO--CO--OC₁₋₄ alkyl; each R₁ andR₂ is methyl; R₄ is R'₄ and R₅ is R'₅ where either R'₄ is --NH--CO-- or--NH--CO--CH₂ --O-- and R'₅ is hydrogen or R'₄ and R'₅ together with thecarbon atom to which they are attached form a group of formula (a) or(b); R₆ is R'₆ and R₇ is R'₇ where either R'₆ is --NH₂, mono- or di-C₁₋₄alkylamino, C₁₋₂ alkylcarbonylamino or benzoylamino and R'₇ is hydrogenor R'₆ and R'₇ together with the carbon atom to which they are attachedform a group of formula (c) or (d); and R₈ is R'₈ where R'₈ is a directbond or --CO--, --CH₂ CO--, --OCH₂ CO-- or --SO₂ --.
 13. A pigmentaccording to claim 8 wherein,R is R' where R' is hydrogen, methyl,formyl, C₁₋₄ alkylcarbonyl or --CO--CO--OC₁₋₄ alkyl; each R₁ and R₂ ismethyl; R₄ is R'₄ and R₅ is R'₅ where either R'₄ is --NH--CO-- or--NH--CO--CH₂ --O-- and R'₅ is hydrogen or R'₄ and R'₅ together with thecarbon atom to which they are attached form a group of formula (a) or(b); R₆ is R'₆ and R₇ is R'₇ where either R'₆ is --NH₂, mono- or di-C₁₋₄alkylamino, C₁₋₂ -alkylcarbonylamino or benzoylamino and R'₇ is hydrogenor R'₆ and R'₇ together with the carbon atom to which they are attachedform a group of formula (c) or (d); and R₈ is R'₈ where R'₈ is a directbond or --CO--, --CH₂ CO--, --OCH₂ CO-- or --SO₂ --.
 14. A pigmentaccording to claim 9 wherein,R is R' where R' is hydrogen, methyl,formyl, C₁₋₄ alkylcarbonyl or --CO--CO--OC₁₋₄ alkyl; each R₁ and R₂ ismethyl; R₄ is R'₄ and R₅ is R'₅ where either R'₄ is --NH--CO-- or--NH--CO--CH₂ --O-- and R'₅ and R'₅ together with the carbon atom towhich they are attached form a group of formula (a) or (b); R₆ is R'₆and R₇ is R'₇ where either R'₆ is --NH₂, mono- or di-C₁₋₄ alkylamino,C₁₋₂ alkylcarbonylamino or benzoylamino and R'₇ is hydrogen or R'₆ andR'₇ together with the carbon atom to which they are attached form agroup of formula (c) or (d); and R₈ is R'₈ where R'₈ is a direct bond or--CO--, --CH₂ CO--, --OCH₂ CO-- or --SO₂ --.
 15. A pigment according toclaim 10 wherein,R is R' where R' is hydrogen, methyl, formyl, C₁₋₄alkylcarbonyl or --CO--CO--OC₁₋₄ alkyl; each R₁ and R₂ is methyl; R₄ isR'₄ and R₅ is R'₅ where either R'₄ is --NH--CO-- or --NH--CO--CH₂ --O--and R'₅ is hydrogen or R'₄ and R'₅ together with the carbon atom towhich they are attached form a group of formula (a) or (b); R₆ is R'₆and R₇ is R'₇ where either R'₆ is --NH₂, mono- or di-C₁₋₄ alkylamino,C₁₋₂ alkylcarbonylamino or benzoylamino and R'₇ is hydrogen or R'₆ andR'₇ together with the carbon atom to which they are attached form agroup of formula (c) or (d); and R₈ is R'₈ where R'₈ is a direct bond or--CO--, --CH₂ CO--, --OCH₂ CO-- or --SO₂ --.
 16. A pigment according toclaim 14 wherein R₁₀ is R'₁₀ where R'₁₀ is hydrogen, methyl, chloro,bromo, C₁₋₂ alkoxy (max. 1 on a phenyl ring) or C₁₋₃ alkoxycarbonyl(max. 1 on a phenyl ring).
 17. A pigment according to claim 15 whereinR₁₀ is R'₁₀ where R'₁₀ is hydrogen, methyl, chloro, bromo, C₁₋₂ alkoxy(max. 1 on a phenyl ring) or C₁₋₃ alkoxycarbonyl (max. 1 on a phenylring).
 18. A pigment according to claim 3 of the formula ##STR56##
 19. Apigment according to claim 4 of the formula ##STR57##
 20. A pigmentaccording to claim 4 of the formula ##STR58##
 21. A pigment according toclaim 4 of the formula ##STR59##
 22. A process for preparing a pigmentaccording to claim 9 comprising reacting a compound of formula XXV

    D--R.sub.30                                                (XXV)

with a compound of formula XXVI or XXVII ##STR60## in which one of R₃₀and R₃₁ is --Cl or --COCl and the other is --R₄ --H or one of R₃₀ andR₃₁ is --R₄ --Cl and the other is hydrogen, and one of R₃₀ and R₃₁ is--COCl or Cl and the other is --R₈ --H or one of R₃₀ and R₃₂ is --R₈--Cl and the other is hydrogen.
 23. A process for preparing a pigmentaccording to claim 14 comprising reacting a compound of formula XXV

    D--R.sub.30                                                (XXV)

with a compound of formula XXVI or XXVII ##STR61## in which one of R₃₀and R₃₁ is --Cl or --COCl and the other is --R₄ --H or one of R₃₀ andR₃₁ is --R₄ --Cl and the other is hydrogen, and one of R₃₀ and R₃₁ is--COCl or Cl and the other is --R₈ --H or one of R₃₀ and R₃₂ is --R₈--Cl and the other is hydrogen.
 24. A process for coloring a polymericmaterial which comprises applying to said material a pigment accordingto claim
 11. 25. A process for coloring a polymeric material whichcomprises applying to said material a pigment according to claim
 14. 26.A process according to claim 24 where the polymeric material ispolyethylene, polypropylene, polystyrene, polyvinylchloride, naturalrubber or synthetic leather.
 27. A process according to claim 25 wherethe polymeric material is polyethylene, polypropylene, polystyrene,polyvinylchloride, natural rubber or synthetic leather.